Eutectic biphenyl-napthalene dye carriers

ABSTRACT

A dye carrier for disperse dyes used on polyester fabrics comprising a eutectic mixture containing large amounts of normally solid biphenyl and normally solid napthalene. The combination of these two normally solid compounds in a ratio of 55-70% by weight biphenyl to 30-45% napthalene becomes a eutectic mixture which lowers the crystallization point of the combination to the range of about 38*-46*C., so that the mixture is much easier to use and handle as a dye carrier when the eutectic mixture is emulsified and solvent is added, so that the combination is a liquid at normal temperature of 60*-95*F. The eutectic mixture of biphenyl and napthalene is an efficient, high strength and economical disperse dye carrier with good lightfastness for use in dyeing synthetic materials such as polyester and triacetates. Where heated storage is available, the eutectic mixture can be stored without added solvent at about 120*F. For convenience, the emulsifier can be added with some further depressing effect on the crystallization temperature of the eutectic mixture. Binary and ternary eutectic mixtures for use in disperse dye carrier formulations are also contemplated including the following: 1. BINARY SYSTEMS, SUCH AS DIPHENYL METHANE/NAPTHALENE; CAMPHOR/NAPTHALENE; NAPTHALENE/M-DINITROBENZENE; DIPHENYL/DIBENZYL; AND BIBENZYL/NAPTHALENE. 2. TERNARY SYSTEMS, SUCH AS BIPHENYL/BIBENZYL/NAPTHALENE. Each of the eutectic systems listed above improves the handling characteristics of the compounds in dye carrier methods because the freezing (solidification) temperature of the combinations are sufficiently low to obtain a liquid system under normal use temperatures.

United States Patent [191 Axon et al.

[ 1 EUTECTIC BlPHENYL-NAPTHALENE DYE CARRIERS [75] Inventors; Gordon L. Axon; Beverly K.

Montezinos, both of Charlotte, NC.

[73] Assignee: Catawba Chemicals, Inc., Charlotte,

[22] Filed: May 23, 1973 [21] Appl. No.: 363,213

[52] 11.5. C1. 8/173; 8/174; 8/175, 8/177 AB [51] lnt. Cl. D06? 5/04 [58] Field of Search... 8/94, 173, 174, 175, 177 AB [56] References Cited UNlTED STATES PATENTS 2,351,046 6/1944 Heymann H 8/174 X 2,362,375 11/1944 Heymannm. 8/174 X 2,362,377 11/1944 Heymann.... 8/174 X 2,394,688 2/1946 Heymann 8/174 X 3,069,219 12/1962 Olpin et al 8/174 X 3,706,530 12/1972 Baumann et a1 8/174 3,728,078 4/1973 Freshwater 8/174 Primary Examiner-Stephen C. Bentley Assistant Examiner-P. A. Nelson 5 7 ABSTRACT A dye carrier for disperse dyes used on polyester fabrics comprising a eutectic mixture containing large amounts of normally solid biphenyl and normally solid napthalene. The combination of these two normally 1 Dec.9,1975

solid compounds in a ratio of -70% by weight biphenyl to 30-45% napthalene becomes a eutectic mixture which lowers the crystallization point of the combination to the range of about 38-46C., so that the mixture is much easier to use and handle as a dye can rier when the eutectic mixture is emulsified and solvent is added, so that the combination is a liquid at normal temperature of -95F. The eutectic mixture of biphenyl and napthalene is an efficient, high strength and economical disperse dye carrier with good lightfastness for use in dyeing synthetic materials such as polyester and triacetates. Where heated storage is available, the eutectic mixture can be stored without added solvent at about F. For convenience, the emulsifier can be added with some further depressing efi'ect on the crystallization temperature of the eutectic mixture.

Binary and ternary eutectic mixtures for use in disperse dye carrier formulations are also contemplated including the following:

1. binary systems, such as diphenyl methane/napthalene; camphor/napthalene; napthalene/m-dinitrobenzene; diphenyl/dibenzyl: and bibenzyl/ napthalene.

2. ternary system. such as napthalene.

hiphenyl/bibenzyl/ Each of the eutectic systems listed above improves the handling characteristics of the compounds in dye carrier methods because the freezing (solidification) temperature of the combinations are sufficiently low to obtain a liquid system under normal use temperatures.

24 Claims, No Drawings EUTECTIC BIPHENYL-NAPTHALENE DYE CARRIERS BACKGROUND OF THE INVENTION The burgeoning use of synthetic materials, such as polyesters and triacetates, in clothing, draperies, tablecloths, upholstery fabrics and carpets, has made necessary a specialized dyeing technology, often referred to as carrier dyeing." Carrier dyeing has replaced acid dyeing techniques used to dye natural fibers, such as wool, because the synthetic fibers do not accept the acid dyes. The same hydrophobic properties which make the synthetic fibers useful also make the older acid dyeing techniques inadequate because the fibers repel the aqueous acid dyes. Carrier dyeing was developed to dye hydrophobic fibers such as polyesters and triacetates with disperse dyes. Once dyed, these fibers have good wetfastness, but the carriers which have been used to accelerate the diffusion of these disperse dyes into the hydrophobic fibers make the carrier dyeing technique considerably more costly than earlier dyeing processes using typical acid dyeing techniques.

Many variations of the disperse dyeing techniques have been tried, and experimentation continues to get the total desirable combination of final product properties at the least possible process cost, because the marketing of synthetic fibers is highly competitive. Dye carrier economies are magnified considerably by the high volume of colored synthetic materials being manufactured.

There are some specific properties which are required in a successful disperse" dye carrier. Included in these properties are those which affect the quality of the finished hydrophobic fiber product such as color depth, wet-fastness and light-fastness. The dye carrier should also have compatibility with all disperse dyes and other auxiliary substances likely to be used. The storage, handling and convenience of use of the dye carrier are other important properties which often determine whether or not a particular dye carrier will be used. The dye carriers which are most wanted are liquids at room temperature to facilitate handling. Biphenyl and naphthalene are both solids at room temperature when not combined with other substances. Biphenyl has been used as a disperse dye carrier in the past in spite of the handling difficulties because it is relatively inexpensive. Naphthalene, however, was not much used for this purpose, possibly because of the problems associated with handling. These two compounds are among the least expensive and most readily available materials which could be used as disperse dye carriers if they could be conveniently handled in a liquid formulation at normal temperatures.

DESCRIPTION OF THE PRIOR ART Messrs. A. Murray and K. Mortimer of Yorkshire Dyeware & Chemical Company, Ltd., Leeds, England recently listed dye carriers in common use, Murray et al., Review of Progress in Coloration, (1971), pp. 67-71. Diphenyl is included in the list, but the authors point out that to avoid crystallization of the carrier in the dye-liquor, it is necessary to add it at a temperature above its melting point (8085C. being required). Naphthalene is not mentioned as a disperse dye carrier here, although it is readily available at relatively low cost, as is biphenyl. Other substances mentioned include methyl cresotinate, butyl benzoate, monomethylnaphthalene, halogenated benzene and diethyl phthalate. Of these, only monomethylnaphthalene, methyl cresotinate and halogenated benzene are considered to be efficient dye carriers for polyester fibers, and these are relatively expensive when compared to biphenyl and naphthalene. The above review by Murray et al. was published in the Journal of the Society of Dyers and Colorists, Vol. 2, May (1971), under the subtitle, Carrier Dyeing.

A general description of disperse dye carrier technique is set forth in US. Pat. No. 3,512,913 issued May 19, 1970 to Day et al. This patent states that it is known to add dye carriers to dye baths and this addition enables dye bath temperatures of -l 10C. The dye carriers there disclosed include phenol, ortho and paraphenylphenol, diphenyl, chlorinated benzenes and diphenyls, methyl salicylate, benzoic acid and benzyl alcohol. This patent is primarily directed to the use of orthoand para-chlorophenols as dye carriers, and it makes no other mention of how diphenyl can be used. The temperatures for the dye bath are in the range of 1580C., and the examples of the preferred embodiments use dye bath temperatures of 40C. Diphenyl has a crystallization temperature far in excess of 40C., and has generally required handling in solid form, as flake biphenyl. Present recommendations for the use of flake biphenyl are for higher temperature (at 160F.) processes which are more difficult to control.

H. M. Friedman described the use of solid dye carriers in combination with water, active carrier chemical and emulsifier base. (American Dyestuff Reporter, Vol. 49, Dec. 12, 1960, page (947).) The carrier mixture required boiling before adding to the dye bath. This writer also observed that the biphenyl was quite sensitive to the amount of emulsifier base present (Ibid. page 104 (951)).

To our knowledge, the eutectic mixture of biphenyl and naphthalene has not previously been used or described for use in a dye carrier formulation. The pure eutectic mixture, without the combination of the invention has been documented. See Lee and Warner, The System Biphenyl-BibenzylNaphthalene, Nearly Ideal Binary and Ternary Systems, American Chemical Society Journal (1935), pages 318-321. The temperatures there recorded for the pure eutectic mixture of biphenyl and naphthalene was about 395C. for a mixture including 0.555 mole fraction of biphenyl, and 0.445 mole fraction of naphthalene. This temperature is about 3C. higher than the eutectic temperature observed by applicants, but the difference can be accounted for based on the purity of the component fractions, and this also accounts for the slightly different ratio of components observed by applicants. Applicants observed the eutectic temperature for 0.575 mole fraction biphenyl with 0.425 mole fraction naphthalene was 36C.

SUMMARY OF THE INVENTION The difficulties associated with the use of normally solid biphenyl and naphthalene as disperse dye carriers for dyeing hydrophobic synthetics such as polyester and triacetate materials have been eliminated by the use of these two compounds in a eutectic mixture with a substantially lower eutectic temperature than the melting point of either biphenyl or naphthalene taken alone. The eutectic mixture can be dissolved in a liquid solvent to produce a mixture which is liquid under normal temperature conditions of storage. To further facilitate handling of the mixture, it can be dissolved in a solvent/emulsifier system for use as a disperse dye carrier. The solvent employed can be selected from aromatic solvents such as xylene, toluene, chlorotoluene and trichlorobenzene. Aromatic esters are also used, including methyl paratoluate, dimethyl phthalate, methyl cresotinate, methyl benzoate, butyl benzoate and methyl dichloro benzoate. The choice of solvent may also include aromatic ethers such as diphenyl oxide and dibenzyl ether. The solvent normally selected is one which is liquid at room temperature, and which is com patible with the emulsifier, dye carrier and the aqueous dye bath system.

The most convenient combination for handling and shipping of this dye carrier composition is the combination in useable proportions of solvent/eutectic mixture. The emulsifier can be added at the time of use, when the aqueous dye carrier system is made up. The principal advantage gained from this combination of solvent and eutectic mixture is to further depress the freezing (solidification) temperature of the combination.

Although it is presently contemplated that the eutectic mixture dye carrier composition of the invention will be mixed with both emulsifier and solvent, it is also possible to obtain the advantages of handling, shipping and storing a liquid biphenyl/naphthalene system by the addition of solvent alone. For example, when a high boiling point aromatic solvent comprising xylene and other higher cut petroleum fractions is mixed in a l:l by weight ratio with the biphenyl/naphthalene eutectic mixture, the crystallization temperature is about 42F, which makes convenient handling in liquid form quite feasible; when the level of eutectic is increased to 70% by weight to 30% by weight of the above xylene solvent, the crystallization temperature is about 59F., still most practical for liquid handling and storage. Other solvents and their effect on crystallization temperature of the biphenyl naphthalene eutectic mixture are listed as follows:

The above tabulation illustrates the direct effect that the selection of solvent and amount used will have on the handling properties of the eutectic mixture dye carrier combination. The emulsifier can be conveniently added at the time of making up the aqueous dye carrier system. In the typical, unheated aqueous dye carrier system using applicants dye carrier, about I pounds of the emulsified dye carrier/solvent mixture is used for each 300 pounds of water (l:3 dilution ratio). When treating a synthetic polyester fabric, about ten pounds of dye carrier should be present for each 100 pounds of fabric being treated, and the weight of aqueous dye carrier solution is usually calculated to be present at about thirty times the weight of the fabric being treated. Typical treating temperatures may range from -l00F., and most treating systems include some apparatus for flexing the fabric or agitating the liquid to insure uniform exposure of all portions of the fabric to the dye carrier solution.

The emulsified, combination dye-carrier can be conveniently applied to the synthetic materials in an aqueous dye bath system at normal temperatures. The disperse dye carriers make the materials being dyed more receptive to the disperse dye colors, with good dye penetration, wetfastness and lightfastness. The emulsified eutectic mixture formulation including solvent in the aqueous system is substantially equivalent in performance to conventional aqueous disperse dye carrier systems, and the eutectic mixture here disclosed is considerably less expensive.

The disadvantages formerly present when biphenyl was used alone have been decreased. The practical use of naphthalene in a disperse dye carrier system has been made much more feasible, and the problems of handling, storing and applying biphenyl and naphthalene as crystalline dye carrier materials have been eliminated.

The utility of the present invention lies in the advantage that a mixture of 55-70% commercial biphenyl in combination with 30-45% commercial naphthalene has a eutectic temperature in the range of 3646C. without any added solvent. This lowered eutectic temperature greatly facilitates handling of these products, because they are in liquid form in the above temperature range, which is only slightly above room temperature. In some handling and storage equipment, it is possible to maintain the eutectic mixture in liquid form by maintaining the temperature above 3646C. It also is contemplated that this mixture, when emulsified, can be added to an aqueous dye carrier system at the slightly elevated temperature to perform the dye carrier function without added solvent.

This eutectic mixture can be used as a dye carrier for synthetic hydrophobic materials such as polyesters and triacetates. In the more typical application, the eutectic mixture is emulsified with an emulsifier, such as a phosphated ethoxylated alcohol, or an ethoxylated linear alcohol. The addition of solvent which is liquid at room temperatures in an amount of about l5-50% by weight of the total mixture will cause the eutectic mixture to become a liquid in the combination. The useful solvents include aromatics such as toluene, chlorotoluene, trichlorobenzene and higher xylenes (which may include a methylnaphthalene fraction). Aromatic esters can also be used, as mentioned above, but some of these are relatively expensive. More typical of these are methyl and butyl benzoates, including an impure fraction of methyl dichlorobenzoate. Diphenyl oxide and dibenzyl oxides are examples of aromatic ether solvents which can be used in the disperse dye carrier combinations of the invention which utilize the advantages of the biphenyl/naphthalene eutectic mixture.

The important function of the solvent is to further depress the freezing temperature of the eutectic mixture so that is a liquid at normal temperatures of use which ordinarily are from about l00F., and preferably about -90F. It has been found that about l5-50% by weight of solvent in the non-aqueous system will accomplish this purpose. The presently preferred solvent is a commercial grade methyl benzoate and it is presently used at about 38-42% by weight of the non-aqueous eutectic mixture system, including also about 53-12% by weight of the emulsifier. The normal melting point for biphenyl is about 6468C., and naphthalene melts at about 76-82C., so it can be seen that the net decrease in melting point achieved by the non-aqueous. emulsified eutectic mixture with added solvent is most significant and practical. This non-aqueous dye-carrier formulation can be formulated, conveniently stored, handled and shipped to the dyeing facilities at normal ambient temperatures of about 65l00F. and even as low as 26F. The water needed in the system can be conveniently added at the dyeing facilities at the time of use, with all the advantages associated with the use of the concentrated liquid emulsion dye carrier, including less bulk as less shipping cost.

It is difficult to compile a list which includes all of the possible emulsifiers which would be used in an aqueous dye carrier system. Some of the criteria involved in the selection of the appropriate emulsifier for the eutectic mixture are: compatibility with the solvent selected, compatibility with the particular synthetic material being dyes, and compatibility with the particular dye. In the event that some residue of the emulsifier remains after the dye carrier treatment, and in those dyeing processes in which the dye carrier system and the dye are present simultaneously, direct compatibility of the dye carrier with the dye is required.

The amount of emulsifier which is used may vary over a wide range, and also is determined by some of the same factors listed above. A convenient method of storing the eutectic mixture dye carrier is in a combination with the emulsifier. In the case of the biphenyl/- naphthalene eutectic mixture, the storage temperature required may in some instances be depressed below the eutectic temperature due to the presence of the particular emulsifier, without requiring the addition of any solvent. This three component dye carrier premix formulation provides a significantly less expensive dye carrier system to the dyeing facility, especially when some transportation distance is involved.

There are many emulsifiers and mixtures which can be used. A partial list includes:

commercially available surfactants and emulsifiers such as;

phosphated and sulfated slcohols (anionic);

alkyl benzene sulfonate (anionic);

phosphated and sulfated ethoxylated alcohols (anionic);

ethoxylated alcohols and alkyl phenols (non-ionic);

ethoxylated organic acids (non-ionic);

ethoxylated ethers and esters of sorbitan and sorbitol (non-ionic);

ethylene oxide/propylene oxide copolymers (nonionic);

and alkanol amides (non-ionic).

The emulsifier presently used is a mixture of a phosphated ethoxylated alcohol (about 6 parts by weight) and an ethoxylated linear alcohol (about 4 parts by weight). The amount of this emulsifier which has been used successfully in the non-aqueous formulation is about 10% by weight, but it is contemplated that the emulsifier could comprise from 1-50% by weight of the non-aqueous system. An other advantage applicants have derived from the use of the eutectic mixture is that it provides a practical means of emulsifying naph- 6 thalene. To applicants knowledge, there was no practical method of emulsifying solid naphthalene.

In a general way, applicants invention is directed to a practical eutectic mixture of at least two compounds which are normally solid at the desired temperature for use in an aqueous dye carrier system. The advantages accrue when the eutectic temperature is below that normally existing under conditions of use and storage. The further lowering of the eutectic temperature can be accomplished by the addition of an appropriate quantity of a normally liquid solvent. It is also possible to form a ternary eutectic mixture. Several other promising eutectic mixtures include diphenyl methane/naphthalene (eutectic temperature (E) 14C.); camphor/- naphthalene (E 323C); naphthale ne/mdinitrobenzene (E at 39C.); 0.450N diphenyl, 0.550 dibenzyl (E 29.5C.); 0.614N bibenzyl, 0.386N naphthalene (E 32.5C.).

The mole fractions of one component in these eutec tic mixtures range from about 0.386 of the first listed compound up to about 0.6l4N. The above eutectics must be evaluated in the specific dye carrier systems with suitable emulsifiers and on the specific fiber for dye carrier effect on dye penetration, color depth, wetfastness and lightfastness. There is also a ternary eutectic of biphenyl, bibenzyl and naphthalene which has a substantially lower eutectic temperature (l7.4C.). This ternary system comprises 0.338 mole fraction biphenyl, 0.392 mole fraction bibenzyl, and 0.270 mole fraction naphthalene. This ternary mixture was de scribed by Lee and Warner ibid. page 320, and the eutectic very closely approaches the ideal for the calculated ternary system. Selection of a dye carrier formulation utilizing a ternary system again depends on the overall cost of the components in the system, and the end results obtained in the synthetic material being dyed.

DETAILED DESCRIPTION OF THE INVENTION The utility of both biphenyl and naphthalene are greatly enhanced for use in disperse dye carrier solvent emulsion systems because biphenyl and naphthalene form a eutectic mixture with a substantially lower eutectic temperature than the crystallization temperature of either compound separately. It is appreciated that the exact melting temperature of the combination can vary to some extent depending on the presence of other substances in the mixture. Applicants presently have observed that the presently preferred biphenyl/naphthalene eutectic mixture is 62% by weight biphenyl to 38% by weight of naphthalene. This mixture has a eutectic temperature of about 36C., which is the lowest presently observed, using commercial grade biphenyl and naphthalene. The above eutectic mixture opens up the possibilities for using both substances where it is important for handling to have a liquid or semi-liquid substance.

This eutectic mixture has proved to be particularly useful as a disperse dye carrier in the dyeing of hydrophobic materials such as polyesters and triacetates. A preferred solvent/eutectic mixture dye carrier/emulsifier for use in disperse dyeing of synthetic materials in aqueous dye bath is set forth below:

E XAMPLE by Wt.

Solvent Biphenyl EXAMPLE-continued by Wt.

Naphthalene l8 .6 Emulsifier Phosphated ethoxylated alcohol 6 Ethoxylated linear alcohol 4 The above example is liquid at 60-95F., and is applied to the synthetic material by the usual treating methods, for example, as by dipping in an aqueous emulsion of the carrier with flexing or other agitation of the synthetic material being dyed. Contact is maintained for a sufficient time to prepare the synthetic material to most effectively absorb the dyes in the dye bath. No heating is required when emulsifying the carrier system of the example, because it is liquid at room temperature. The above formulation provides an advantage because it greatly facilitates the emulsification of naphthalene, which would otherwise normally be a solid at the temperatures here used (60-95F.).

The above liquid dye carrier formulation was used in standard dye tests on polyester materials including blends, and the dyed materials were tested for light fastness, wet fastness and other properties such as handle" were evaluated. ln these tests, the dye carrier formulation of the invention using the eutectic mixture of biphenyl and naphthalene performed as well as standard commercial dye carrier formulations which are considerably more costly. The dye color used in these tests was Eastman fast blue (B-GLF) Color Index No. 60,767, Disperse Blue 27, available from Eastman Chemical Company, Rochester, New York. A polyester/cotton fiber blend was dyed using the above dye carrier formulation in an aqueous system. The dyed swatches exhibited excellent lightfastness, handle was observed to be superior, and color depth appeared complete. The same results were obtained when the above dye carrier formulation in an aqueous system was used on 100% synthetic fiber yarns woven together in cut pile carpet swatches. The high bulk polyester yarns received the blue dye to give an excellent, deep and uniform blue color to the swatches tested.

In the typical aqueous system, the dye carrier mixture is emulsified, and solvent is added. ()ne part of this emulsifier/solvent/eutectic mixture formulation is then added to three parts of water at l l-l40F. with mixing, and agitated for about 3-5 minutes. The resulting aqueous emulsion dye carrier system can then be used in a two-stage bath system as described in U.S. Pat. No. 3,512,913 issued May I9, 1970 and in other aqueous immersion systems, either continuous or batch type. The above eutectic mixture dye carrier system with solvent added can be conveniently stored and handled at temperatures as a liquid at temperatures in the range of 6095F.

We claim:

1. A aqueous dye carrier composition for dyeing syn- :hetic materials including polyesters and triacetates :omprising in combination a solvent, emulsifier, and a :utectic mixture of biphenyl and naphthalene comprisng 55-70% by weight biphenyl, and 30-45% by weight iaphthalene, said eutectic mixture having a eutectic vemperature in the range of 36-46C., said dye carrier :omposition including sufficient solvent so that the :ombination remains in liquid form at temperatures elow 36C.

2. The composition of claim 1, including sufficient solvent to maintain the combination in liquid form at normal temperatures of use in the range of 60l00F.

3. The composition of claim 1, in which the solvent is selected from the group consisting of aromatic solvents including xylene, toluene, chlorotoluene and trichlorobenzene; aromatic esters including methyl paratoluate, dimethyl phthalate, methyl cresotinate, methyl benzoate, butyl benzoate and methyl dichlorobenzoate; and aromatic ethers including diphenyl oxide and dibenzyl ether.

4. The composition of claim 3, in which the solvent comprises 15-50% by weight of the combination.

5. The composition of claim 4, in which the solvent is methyl benzoate and is present in the amount of about 38-42% by weight of the total composition.

6. The composition of claim I, in which the emulsifier is present in the amount of l to 50% by weight of the total combination.

7. The composition of claim 1, in which the emulsifier comprises about 5- l 5% by weight of the total mixture.

8. The composition of claim 1, in which the emulsifier is selected from the group consisting of commercially available surfactants and emulsifiers such as; phosphated and sulfated alcohols (anionic); alkyl benzene sulfonate (anionic); phosphated and sulfated ethoxylated alcohols (anionic); ethoxylated alcohols and alkyl phenols (nonionic); ethoxylated organic acids (non-ionic); ethoxylated ethers and esters of sorbitan and sorbitol (non-ionic); ethylene oxide/propylene oxide copolymers (non-ionic); and alkanol amides (non-ionic).

9. An aqueous dye carrier composition for dyeing synthetic materials including polyesters and triacetates, comprising in combination a solvent, an emulsifier present at 8-12% by weight of the total combination and comprising a mixture of phosphated ethoxylated alcohol and an ethoxylated linear alcohol, and a eutectic mixture of biphenyl and naphthalene, said eutectic mixture comprising 55-70% by weight biphenyl and 30-45% by weight naphthalene, said eutectic mixture having a eutectic temperature in the range of 3646C., and said dye carrier composition including sufiicient solvent so that the combination remains in liquid form at temperatures below 36C.

10. The composition of claim 9, in which sufiicient water is present to provide an aqueous dye carrier solution.

11. The composition of claim 10, in which there is one part of the dye carrier composition mixed with three parts of water, said aqueous dye carrier system so formed being in liquid form at temperatures in the range of 60l00F.

12. A premixed combination of substances for use as an aqueous disperse dye carrier system for dyeing synthetic materials including polyesters and triacetates, said combination comprising a eutectic mixture of biphenyl and naphthalene, and an emulsifier for said eutectic mixture to facilitate dispersion of said eutectic mixture in the aqueous dye carrier system.

13. The premixed combination of claim 12 comprising about 1-50% of an emulsifier selected from the group consisting of commercially available surfactants and emulsifiers such as; phosphated and sulfated alcohols (anionic); alkyl benzene sulfonate (anionic); Phosphated and sulfated ethoxylated alcohols (anionic); ethoxylated alcohols and alkyl phenols (non-ionic ethoxylated organic acids (non-ionic); ethoxylated ethers and esters of sorbitan and sorbitol (non-ionic); ethylene oxide/propylene oxide copolymers (nonionic); and alkanol amides (non-ionic).

14. The premixed combination of claim 12 comprising about -30% of an emulsifier comprising a mixture of phosphated ethoxylated alcohol and an ethoxylated linear alcohol, and is present in the total combination in the amount of 8-1 2% by weight.

15. A disperse dye carrier composition for use in disperse dyeing of hydrophobic materials including polyesters and triacetates comprising a eutectic mixture selected from the group consisting of diphenyl methane/- naphthalene, camphor/naphthalene, naphthalene/mdinitrobenzene, diphenyl/dibenzyl, bibenzyl/naphthalene and a ternary system including biphenyl/bibenzylI- naphthalene, in combination with an emulsifier for said eutectic mixture capable of forming an emulsion therewith which is stable in water.

16. The disperse dye carrier composition of claim 15, in which the emulsifier is selected from the group consisting of commercially available surfactants and emulsifiers such as; phosphated and sulfated alcohols (anionic); alkyl benzene sulfonate (anionic); phosphated and sulfated ethoxylated alcohols (anionic); ethoxylated alcohols and alkyl phenols (non-ionic); ethoxylated organic acids (non-ionic); ethoxylated ethers and esters of sorbitan and sorbitol (non-ionic); ethylene oxide/propylene oxide copolymers (non-ionic); and alkanol amides (non-ionic).

17. The disperse dye carrier of claim 16, in which the solvent is selected from the group consisting of aromatic solvents including toluene, chlorotoluene trichlorobenzene, higher xylenes, aromatic esters including methyl para toluate, dimethyl phthalate, methyl cresotinate, methyl benzoate and butyl benzoate, methyl dichloro benzoate, aromatic ethers including diphenyl oxide and dibenzyl oxide and mixtures thereof, which is compatible with the emulsified eutectic mixture and water.

18. A disperse dye carrier composition comprising, in combination, a eutectic mixture of biphenyl and naphthalene comprising 55-70% by weight biphenyl and 30-45% by weight naphthalene, said eutectic mixture having a eutectic temperature in the range of 3646C., and a solvent for said eutectic mixture for maintaining said eutectic mixture in a liquid state at temperatures below 36C., said solvent being selected from the group consisting of toluene, xylene, chlorotoluene, trichlorobenzene, methyl paratoluate, dimethyl phthalate, methyl cresotinate, methyl benzoate, butyl benzoate, methyl dichloro benzoate, diphenyl oxide, dibenzyl ether, said solvent/eutectic mixture being in liquid form at temperatures below 36C.

19. The composition of claim 18, including an emulsifier for said eutectic mixture to facilitate dispersion of said solvent/eutectic mixture in an aqueous dye carrier system, said emulsifier being selected from the group consisting of commercially available surfactants and emulsifiers such as; phosphated and sulfated alcohols (anionic); alkyl benzene sulfonate (anionic); phosphated and sulfated ethoxylated alcohols (anionic); ethoxylated alcohols and alkyl phenols (non-ionic); ethoxylated organic acids (non-ionic); ethoxylated ethers and esters of sorbitan and sorbitol (non-ionic); ethylene oxide/propylene oxide copolymers (nonionic); and alkanol amides (non-ionic).

20. The composition of claim 19, in which the emulsified solvent/eutectic mixture is dispersed in an aqueous dye carrier system at the ratio of about I00 pounds emulsified solvent/eutectic mixture to about 300 pounds of water.

21. An aqueous dye carrier composition comprising, in combination, a eutectic mixture of biphenyl and naphthalene comprising 5570% by weight biphenyl and 30-45% by weight naphthalene, said eutectic mixture having a eutectic temperature in the range of 3646C., a solvent selected from the group consisting of toluene, xylene, chloro-toluene, trichlorobenzene, methyl paratoluate, dim ethyl phthalate, methyl cresotinate, methyl benzoate, butyl benzoate, methyl dichlorobenzoate, diphenyl oxide, dibenzyl ether for maintaining said eutectic mixture in a liquid state at temperatures below 36C., an emulsifier selected from the group consisting of phosphated and sulfated alcohols (anionic), alkyl benzene sulfonate (anionic), phosphated ans sulfated ethoxylated alcohols (anionic), ethoxylated alcohols and alkyl phenols (non-ionic), ethoxylated organic acids (non-ionic); ethoxylated ethers and esters of sorbitan and sorbitol (non-ionic), ethylene oxide/propylene oxide copolymers (nonionic), alkanol amides (non-ionic) and mixtures of phosphated ethoxylated alcohol and an ethoxylated linear alcohol, said emulsifier comprising 8-12% by weight of the emulsified solvent/eutectic mixture portion of the aqueous dye carrier system and the selected solvent comprising at least 40% by weight of the weight of the solvent/eutectic mixture.

22. In an aqueous dye carrier system for dyeing synthetic fabrics and materials including polyesters and triacetates a eutectic mixture comprising normally solid biphenyl and naphthalene in a ratio of 55-70% by weight biphenyl to 30-45% by weight naphthalene, said eutectic mixture having a eutectic temperature in the range of 3646C., and when combined with solvent, said eutectic mixture remaining liquid at temperatures below 36C.

23. The aqueous dye carrier system of claim 22, including as the solvent a mixture of phosphated ethoxylated alcohol and an ethoxylated linear alcohol.

24. The aqueous dye carrier system of claim 23, including an emulsifier selected from the group consisting of anionic surfactants and non-ionic surfactants. 

1. A AQUEOUS DYE CARRIER COMPOSITION FOR DYEING SYNTHETIC MATERIALS INCLUDING POLYESTERS AND TRIACETATES COMPRISING IN COMBINATION A SOLVENT, EMULSIFIER, AND A EUTECTIC MIXTURE OF BIPHENYL AND NAPHTHALENE COMPRISING 55-70% BY WEIGHT BIPHENYL AND 30-45% BY WEIGHT NAPHTHALENE, SAID EUTECTIC MIXTURE HAVING A EUTECTIC TEMPERATURE IN THE RANGE OF 36*-46*C, SAID DYE CARRIER COMPOSITION INCLUDING SUFFICIENT SOLVENT SO THAT THE COMBINATION REMAINS IN LIQUID FORM AT TEMPERATURES BELOW 36*C.
 2. The composition of claim 1, including sufficient solvent to maintain the combination in liquid form at normal temperatures of use in the range of 60*-100*F.
 3. The composition of claim 1, in which the solvent is selected from the group consisting of aromatic solvents including xylene, toluene, chlorotoluene and trichlorobenzene; aromatic esters including methyl paratoluate, dimethyl phthalate, methyl cresotinate, methyl benzoate, butyl benzoate and methyl dichlorobenzoate; and aromatic ethers including diphenyl oxide and dibenzyl ether.
 4. The composition of claim 3, in which the solvent comprises 15-50% by weight of the combination.
 5. The composition of claim 4, in which the solvent is methyl benzoate and is present in the amount of about 38-42% by weight of the total composition.
 6. The composition of claim 1, in which the emulsifier is present in the amount of 1 to 50% by weight of the total combination.
 7. The composition of claim 1, in which the emulsifier comprises about 5-15% by weight of the total mixture.
 8. The composition of claim 1, in which the emulsifier is selected from the grouP consisting of commercially available surfactants and emulsifiers such as; phosphated and sulfated alcohols (anionic); alkyl benzene sulfonate (anionic); phosphated and sulfated ethoxylated alcohols (anionic); ethoxylated alcohols and alkyl phenols (non-ionic); ethoxylated organic acids (non-ionic); ethoxylated ethers and esters of sorbitan and sorbitol (non-ionic); ethylene oxide/propylene oxide copolymers (non-ionic); and alkanol amides (non-ionic).
 9. An aqueous dye carrier composition for dyeing synthetic materials including polyesters and triacetates, comprising in combination a solvent, an emulsifier present at 8-12% by weight of the total combination and comprising a mixture of phosphated ethoxylated alcohol and an ethoxylated linear alcohol, and a eutectic mixture of biphenyl and naphthalene, said eutectic mixture comprising 55-70% by weight biphenyl and 30-45% by weight naphthalene, said eutectic mixture having a eutectic temperature in the range of 36*-46*C., and said dye carrier composition including sufficient solvent so that the combination remains in liquid form at temperatures below 36*C.
 10. The composition of claim 9, in which sufficient water is present to provide an aqueous dye carrier solution.
 11. The composition of claim 10, in which there is one part of the dye carrier composition mixed with three parts of water, said aqueous dye carrier system so formed being in liquid form at temperatures in the range of 60*-100*F.
 12. A premixed combination of substances for use as an aqueous disperse dye carrier system for dyeing synthetic materials including polyesters and triacetates, said combination comprising a eutectic mixture of biphenyl and naphthalene, and an emulsifier for said eutectic mixture to facilitate dispersion of said eutectic mixture in the aqueous dye carrier system.
 13. The premixed combination of claim 12 comprising about 1-50% of an emulsifier selected from the group consisting of commercially available surfactants and emulsifiers such as; phosphated and sulfated alcohols (anionic); alkyl benzene sulfonate (anionic); phosphated and sulfated ethoxylated alcohols (anionic); ethoxylated alcohols and alkyl phenols (non-ionic); ethoxylated organic acids (non-ionic); ethoxylated ethers and esters of sorbitan and sorbitol (non-ionic); ethylene oxide/propylene oxide copolymers (non-ionic); and alkanol amides (non-ionic).
 14. The premixed combination of claim 12 comprising about 10-30% of an emulsifier comprising a mixture of phosphated ethoxylated alcohol and an ethoxylated linear alcohol, and is present in the total combination in the amount of 8-12% by weight.
 15. A disperse dye carrier composition for use in disperse dyeing of hydrophobic materials including polyesters and triacetates comprising a eutectic mixture selected from the group consisting of diphenyl methane/naphthalene, camphor/naphthalene, naphthalene/m-dinitrobenzene, diphenyl/dibenzyl, bibenzyl/naphthalene and a ternary system including biphenyl/bibenzyl/naphthalene, in combination with an emulsifier for said eutectic mixture capable of forming an emulsion therewith which is stable in water.
 16. The disperse dye carrier composition of claim 15, in which the emulsifier is selected from the group consisting of commercially available surfactants and emulsifiers such as; phosphated and sulfated alcohols (anionic); alkyl benzene sulfonate (anionic); phosphated and sulfated ethoxylated alcohols (anionic); ethoxylated alcohols and alkyl phenols (non-ionic); ethoxylated organic acids (non-ionic); ethoxylated ethers and esters of sorbitan and sorbitol (non-ionic); ethylene oxide/propylene oxide copolymers (non-ionic); and alkanol amides (non-ionic).
 17. The disperse dye carrier of claim 16, in which the solvent is selected from the group consisting of aromatic solvents including toluene, chlorotoluene trichlorobenzene, higher xylenes, aromatic esters includIng methyl para toluate, dimethyl phthalate, methyl cresotinate, methyl benzoate and butyl benzoate, methyl dichloro benzoate, aromatic ethers including diphenyl oxide and dibenzyl oxide and mixtures thereof, which is compatible with the emulsified eutectic mixture and water.
 18. A disperse dye carrier composition comprising, in combination, a eutectic mixture of biphenyl and naphthalene comprising 55-70% by weight biphenyl and 30-45% by weight naphthalene, said eutectic mixture having a eutectic temperature in the range of 36*-46*C., and a solvent for said eutectic mixture for maintaining said eutectic mixture in a liquid state at temperatures below 36*C., said solvent being selected from the group consisting of toluene, xylene, chlorotoluene, trichlorobenzene, methyl paratoluate, dimethyl phthalate, methyl cresotinate, methyl benzoate, butyl benzoate, methyl dichloro benzoate, diphenyl oxide, dibenzyl ether, said solvent/eutectic mixture being in liquid form at temperatures below 36*C.
 19. The composition of claim 18, including an emulsifier for said eutectic mixture to facilitate dispersion of said solvent/eutectic mixture in an aqueous dye carrier system, said emulsifier being selected from the group consisting of commercially available surfactants and emulsifiers such as; phosphated and sulfated alcohols (anionic); alkyl benzene sulfonate (anionic); phosphated and sulfated ethoxylated alcohols (anionic); ethoxylated alcohols and alkyl phenols (non-ionic); ethoxylated organic acids (non-ionic); ethoxylated ethers and esters of sorbitan and sorbitol (non-ionic); ethylene oxide/propylene oxide copolymers (non-ionic); and alkanol amides (non-ionic).
 20. The composition of claim 19, in which the emulsified solvent/eutectic mixture is dispersed in an aqueous dye carrier system at the ratio of about 100 pounds emulsified solvent/eutectic mixture to about 300 pounds of water.
 21. An aqueous dye carrier composition comprising, in combination, a eutectic mixture of biphenyl and naphthalene comprising 55-70% by weight biphenyl and 30-45% by weight naphthalene, said eutectic mixture having a eutectic temperature in the range of 36*-46*C., a solvent selected from the group consisting of toluene, xylene, chloro-toluene, trichlorobenzene, methyl paratoluate, dimethyl phthalate, methyl cresotinate, methyl benzoate, butyl benzoate, methyl dichlorobenzoate, diphenyl oxide, dibenzyl ether for maintaining said eutectic mixture in a liquid state at temperatures below 36*C., an emulsifier selected from the group consisting of phosphated and sulfated alcohols (anionic), alkyl benzene sulfonate (anionic), phosphated ans sulfated ethoxylated alcohols (anionic), ethoxylated alcohols and alkyl phenols (non-ionic), ethoxylated organic acids (non-ionic); ethoxylated ethers and esters of sorbitan and sorbitol (non-ionic), ethylene oxide/propylene oxide copolymers (non-ionic), alkanol amides (non-ionic) and mixtures of phosphated ethoxylated alcohol and an ethoxylated linear alcohol, said emulsifier comprising 8-12% by weight of the emulsified solvent/eutectic mixture portion of the aqueous dye carrier system and the selected solvent comprising at least 40% by weight of the weight of the solvent/eutectic mixture.
 22. In an aqueous dye carrier system for dyeing synthetic fabrics and materials including polyesters and triacetates a eutectic mixture comprising normally solid biphenyl and naphthalene in a ratio of 55-70% by weight biphenyl to 30-45% by weight naphthalene, said eutectic mixture having a eutectic temperature in the range of 36*-46*C., and when combined with solvent, said eutectic mixture remaining liquid at temperatures below 36*C.
 23. The aqueous dye carrier system of claim 22, including as the solvent a mixture of phosphated ethoxylated alcohol and an ethoxylated linear alcohol.
 24. The aqueous dye carrier system of claim 23, including an emulsifier selected from the group consisting of anionic surfactants and non-ionic surfactants. 